Antioxidant combinations of molybdenum complexes and aromatic amine compounds

Abstract

An antioxidant additive combination for lubricating oils is prepared by combining (a) a sulfur containing molybdenum compound prepared by reacting an acidic molybdenum compound, a basic nitrogen compound, and a sulfur compound, with (b) an aromatic amine compound.

What is claimed is: 
     
       1. A lubricating oil additive comprising a combination of (a) an oil soluble sulfur containing molybdenum complex prepared by (1) reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a succinimide, carboxylic acid amide, Mannich base, phosphonamide, thiophosphonamide, phosphoramide, dispersant viscosity index improvers, or mixtures thereof to form a molybdenum complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom, and (2) reacting said complex with a sulfur containing compound in an amount to provide 0.1 to 4 atoms of sulfur per atom of molybdenum, and   (b) an oil soluble aromatic amine compound or mixtures thereof, wherein the aromatic amine compound of component (b) is present in an amount of from 0.02 to 10 parts by weight per part by weight of the sulfur containing molybdenum complex of component (a).   
     
     
       2. The oil additive of claim 1 wherein the aromatic amine of component (b) is selected from the group consisting of an N-aryl amine and an N,N'-arylene diamine. 
     
     
       3. The oil additive of claim 2, wherein the N-aryl-amine has the formula ##STR7## wherein R 1  and R 2  are the same or different and each is hydrogen, alkyl of 1 to 18 carbon atoms, aryl of 6 to 14 carbon atoms, alkaryl of 7 to 34 carbon atoms or aralkyl of 7 to 12 carbon atoms; R 3  is aryl of 6 to 14 carbon atoms or alkaryl of 7 to 34 carbon atoms. 
     
     
       4. The oil additive of claim 2 wherein the N,N'-arylene diamine has the formula ##STR8## wherein R 4 , R 5 , R 6  and R 7  are the same or different and each is hydrogen, alkyl of 1 to 12 carbon atoms, aryl, aralkyl, or alkaryl having from 6 to 22 carbon atoms, and B is selected from the group consisting of arylene containing 6 to 14 carbon atoms and a group of the formula ##STR9## wherein X is a covalent bond, alkylene containing 1 to 8 carbon atoms, --O--, --CO--, --S--, or --SO 2  --. 
     
     
       5. The additive of claim 2 wherein the N-arylamine is selected from the group consisting of N-phenyl-alphanaphthylamine, p,p'-dioctyldiphenylamine and diisobornyldiphenylamine. 
     
     
       6. The oil additive of claim 1 wherein the sulfur source used to prepare the molybdenum complex of component (a) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R 2  S x  where R is hydrocarbyl, and x is at least 2, inorganic sulfides or inorganic polysulfides, thioacetamide, thiourea, mercaptans of the formula RSH where R is hydrocarbyl, or a sulfur-containing antioxidant. 
     
     
       7. The oil additive of claim 6 wherein the sulfur source used to prepare the molybdenum complex of component (a) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R 2  S x  where R is C 1-40  hydrocarbyl, and x is at least 3, inorganic sulfides, or inorganic polysulfides, thioacetamide, thiourea or RSH where R is C 1-40  alkyl, and the acidic molybdenum compound is molybdic acid, molybdenum trioxide, or ammonium molybdate. 
     
     
       8. The oil additive of claim 7 wherein the sulfur source used to prepare the molybdenum complex of component (a) is sulfur, hydrogen sulfide, RSH where R is C 1-10  alkyl, phosphorus pentasulfide, or (NH 4 ) 2  S x' , where x' is at least 1, said acidic molybdenum compound is molybdic acid, molybdenum trioxide, or ammonium molybdate, and said basic nitrogen compound is a succinimide, carboxylic acid amide, or Mannich base. 
     
     
       9. The oil additive of claim 8 wherein said basic nitrogen compound is a C 24-350  hydrocarbyl succinimide, carboxylic acid amide, or a Mannich base prepared from a C 9-200  alkylphenol, formaldehyde, and an amine. 
     
     
       10. The oil additive of claim 9 wherein said basic nitrogen compound is a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentaamine or triethylene tetraamine. 
     
     
       11. The oil additive of claim 9 wherein said basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of the formula R 2  COOH, or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, wherein R 2  is C 12-350  alkyl or C 12-350  alkenyl and a hydrocarbyl polyamine. 
     
     
       12. The oil additive of claim 11 wherein R 2  is C 12-20  alkyl or C 12-20  alkenyl and the hydrocarbyl polyamine is tetraethylene pentaamine or triethylene tetraamine. 
     
     
       13. The oil additive of claim 8 wherein said basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamine. 
     
     
       14. The additive of claim 9 wherein said basic nitrogen compound is a Mannich base prepared from C 80-100  alkylphenol, formaldehyde and triethylene tetraamine, or tetraethylene pentaamine, or mixtures thereof. 
     
     
       15. The oil additive of claim 1 comprising a combination of (a) an oil soluble sulfur containing molybdenum complex prepared by (1) reacting a C 24-350  hydrocarbyl succinimide, and an acidic molybdenum compound selected from the group consisting of molybdic acid, molybdenum trioxide and ammonium molybdate, and (2) reacting said complex with a sulfur compound selected from the group consisting of sulfur and hydrogen sulfide, and (b) an oil soluble aromatic amine compound selected from the group consisting of N-phenyl-alpha-naphthylamine, p,p'-dioctyldiphenylamine and diisobornyldiphenylamine. 
     
     
       16. The oil additive of claim 15 wherein the hydrocarbyl succinimide is a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentaamine or triethylene tetraamine, the sulfur source used to prepare the molybdenum complex is sulfur. 
     
     
       17. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05 to 15 percent by weight of the additive of claim 1, 2 or 3. 
     
     
       18. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15 to 90 percent by weight of the product of claim 1, 2 or 3.